Chemical Tanker Operations for the STCW Advanced Training Course

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This publication is a comprehensive guide to chemical tanker cargo operations. It is an essential reference point for serving officers and managers, as well as those undertaking advanced training as required by the STCW Convention. Fully illustrated throughout with colour photographs and annotated diagrams, it covers topics such as international regulations, cargo handling and hazards, environmental protection, emergency response, safety management, tank cleaning and ship design and equipment.

The contents do not challenge the established in-depth guidance of other industry organisations, but provides a cross-reference to those publications to ensure an overall understanding of safe chemical tanker operations.

The book is written as a practical sequential prompt, an aide-mémoire for serving officers and managers, and as a consolidated study guide for those undertaking the advanced training for chemical tanker cargo operations as required by the STCW Convention.

Chemical Tanker Operations for the STCW Advanced Training Course provides a wealth of information, ideal for serving officers and managers, as well as those undertaking advanced training as required by the STCW Convention. Elements of chemical tanker operations covered include:

Each chapter ends with helpful references to relevant regulations, codes and industry guidelines and the publication is supported by appendices covering the carriage and handling of vegetable and animal oils and fats (as characterised as noxious liquid substances under MARPOL Annex II) and tank cleanliness assessments for high specification cargoes.

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3 1 Introduction 1.1 Purpose and Scope This book is not an Industry Standard or Code of Practice. The contents do not challenge the established in-depth guidance of other industry organisations, but provide a cross- reference to those publications to ensure an overall understanding of safe chemical tanker operations. The book is written as a practical sequential prompt, an aide-mémoire for serving officers and managers, and as a consolidated study guide for those undertaking the advanced training for chemical tanker cargo operations as required by the STCW Convention. The book assumes that the reader has successfully completed basic training for oil and chemical tanker cargo operations. 1.2 General Introduction Bulk liquid chemicals have been carried on tankers since the early 1950’s. Predominantly using oil tankers, the trade was driven by the needs of chemical companies to move feed stock cargoes from the oil company refineries to the chemical processing and production plants around the world. Ships used by those pioneering companies in this new trade were predominantly oil tankers, and not the complex chemical tankers that serve the trade today. Most feedstock cargoes are solvents and the then single hulled riveted ships were not conducive to safe carriage. Furthermore, the limited cargo handling capabilities, designed for one or two grades of oil, could not provide the required segregation for multiple products. Ahead of any international legislation, the pioneering companies had the foresight to see the necessity of purposeful built ships to carry the ever increasing numbers of bulk chemical cargoes, both safely and in a commercially efficient way. The new ocean going ships were single hulled with wing cargo tanks protecting the centre tanks and constructed with double bottom segregated ballast tanks. Smaller coastal ships were built with double hulls and stainless steel was used for cargo tanks and pumping systems to carry the growing volume of acid cargoes. All the ships had relatively small tanks with the vision of carrying smaller parcels as required by the customers, therefore eliminating the number of slack tanks and optimising the carrying capacity. The operators of the early ships also recognised the need for cargo segregation, providing tanks with individual cargo pumps or installing bulkhead sluice valves which allowed pairs of tanks to share the pump. Similarly, the design of the venting systems provided sets of cargo tanks with vapour segregation, and pressure control was maintained by the fitting of pressure/ vacuum relief valves. It was also realised that having to open tanks for ullaging was somewhat of a contradiction of the ingenious design, therefore enclosed gauging was incorporated, and all of this was before the BCH Code. Unfortunately, some of the early equipment originated from the storage terminal industry and the designs were not always conducive to marine transportation; ship movement, salt water and corrosion was a major issue affecting reliability. However, the ship operators worked with the equipment manufactures and this collaboration of experience solved the problems, providing the safe, heavy weather proof and reliable equipment that is installed on modern chemical tankers. A similar reliability scenario would be encountered again with the introduction of automated digital technology. The BCH Code was introduced under the SOLAS 1974 Convention, and later the IBC Code became applicable to all ships built after 1st July 1986. MARPOL Annex II entered into force in 1987 and the 1989 amendments harmonised the Appendices with the IBC Code. This mandatory international legislation, supported by the industry vetting inspection, maintains the high operating standards that are 4 Chemical Tanker Operations for the STCW Advanced Training Course the expected norm for bulk chemical shipping today. In the early days bulk chemical cargoes were predominately feedstocks for the production of processed chemicals and the finished high grade products were shipped in smaller packaged quantities. However, the operational performance of chemical tankers proved exemplary and the modern ship designs coupled with reliability of service offered the chemical producers the possibility of shipping high grade finished products in bulk by sea. This prompted change in the geography of chemical production; no longer did the production plant rely on the long distance supply of feedstock, but production could be relocated closer to the feedstock producers, and the finished high grade products could be shipped in bulk to the end user. Today, chemical tankers often discharge their cargoes directly into the production line. This carries considerable liability for the ship operator and it is essential that all cargo quality controls are in place from the voyage planning stages through to the completion of discharge. Maintaining the cargo specification is critical and explains the thorough inspection and analysis that is now common place. Of the three types of tankers (oil, chemical and gas), it is the chemical tanker that has had to continuously evolve as new chemicals present a constantly changing set of carriage criteria to which the ship design and operation should comply. Meeting these changes and challenges requires experienced officers and crew, constantly alert to changes and managing those changes. Quite possibly, the most important element in ensuring the operating performance of a chemical tanker is the knowledge and experience of the officers and crew. The Master is reliant on the competency of officers and crew, not least the engineering department who maintain the systems that allow the ship to operate safe and efficiently. 1.3 The STCW Requirement The advanced training for chemical tanker cargo operations requires the candidate to demonstrate competence in the following: yyAbility to safely perform and monitor all cargo operations yyfamiliarity with physical and chemical properties of chemical cargoes yyprecautions to prevent hazards yyapplication of occupational health and safety precautions yyresponse to emergencies yyprecautions to prevent pollution of the environment yymonitor and control compliance with legislative requirements. Chapter 1 Regulations, Codes and Industry Guidelines STCWTSG Chapter 3 7 2 Chemical Cargoes and the Basic Chemistry 2.1 Chemical Cargo Groups Throughout this book, in legislation and industry publications, words are used to indicate that individual chemicals belong to: families, categories, classes or grades. As each description arises, it is important to differentiate between the true meaning and application of each description, so that on reading the text, the reader can immediately recognise the context in which the chemical is being discussed and avoid any misunderstanding. Chemical groups refer to the origin of the chemical, where it came from and the process through which it has evolved. There are just four chemical cargo groups: 1. PETROCHEMICALS 2. ORGANIC CHEMICALS 3. INORGANIC CHEMICALS 4. VEGETABLE AND ANIMAL OILS AND FATS As suggested, there are many other groupings/ categorizations of chemicals in the maritime industry based on health, safety and environmental hazards; these should not be confused with the above. Petrochemicals Petrochemicals are hydrocarbons, which are compounds of carbon and hydrogen. All hydrocarbons have a carbon “backbone”, which may be straight, branched or even be a ring; hydrogen atoms are attached to that backbone in varying numbers, giving rise to the chemical formula. Petrochemicals originate from crude oil or coal. Examples are: yyBenzene yyToluene yyP-Xylene Organic Chemicals Organic chemicals are also hydrocarbons having the same carbon backbone with hydrogen atoms attached. However, organic chemicals mostly originate from living organisms such as wood, vegetation or animals and often extracted through a process of fermentation. Organic chemicals are commonly labelled Alcohols or Carbohydrates. Examples are: yyAlcohols yyNitrites yyUrea Inorganic Chemicals If the organic chemicals are removed from the list of compounds, the remainder may be described as inorganic. Inorganic chemicals do not (in general) contain carbon atoms, the exceptions include: carbides, carbonates and cyanides. Inorganic chemicals do not originate from living or dead organisms; they are often the by-product of another industry but are an extremely important component in chemical production, used as catalysts, pigments and surfactants. Examples are: yyAcids yyCalcium yyPhosphorous Vegetable and Animal Oils and Fats Vegetable and animal oils and fats are common bulk liquid cargoes carried on chemical tankers. In crude form, these cargoes originate from processing the seeds of vegetation and animal carcases to produce biological oil and fat feedstocks. Refining the crude feedstock cargoes is the basis for the production of oleochemicals, which have a wide range of applications in many industries, food processing and biofuel. Examples are: yyPalm oil yyRape seed oil yyTallow yyFatty acids (oleochemical) yyGlycerine (oleochemical) yyMethyl esters (oleochemical) 8 Chemical Tanker Operations for the STCW Advanced Training Course 2.1.1 Chemical Gases Though not shipped in bulk on chemical tankers, it is important to recognize the importance of chemical gases in the manufacture of chemical products. Many chemical gases form the basic feedstock and are referenced in the following section on basic chemistry. Gas, liquid and solid are the three states of matter or material. A solid has a definite shape and volume, a liquid has a definite volume but takes the shape of the container, and a gas has no defined shape or volume. Examples of chemical gases include: yyEthylene yyMethane yyPropylene yyButylene yyButadiene There are several cargoes that are covered by both the IBC and IGC Codes, these include: yyDiethyl Ether yyIsoprene yyIsopropylamine yyMonoethylamine (Ethylamine) yyPentane (all isomers) yyPentene (all isomers) yyPropylene Oxide yyVinyl Ethyl Ether yyVinylidene Chloride These cargoes can be shipped in both chemical tankers and gas tankers that are constructed and equipped to meet the minimum and special requirements as specified in the IBC and IGC Codes respectively. 2.1.2 Oil or Noxious Liquid Substance? Pages could be written in attempting to ultimately define oil and noxious liquid substance, however the individual opinions of eminent chemists will always differ. The term used for chemicals in the maritime industry is NLS (Noxious Liquid Substance). The transportation of NLS in bulk by sea is legislated by the IMO and substances are defined by the Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection (GESAMP). GESAMP is jointly sponsored by nine UN organizations with responsibilities relating to the marine environment. Simply, if GESAMP define a substance as a NLS, then all the member States make it a NLS and carriage should comply with the International Code for the Construction and Equipment of Ships carrying Dangerous Chemicals in Bulk (IBC Code). Oil cargoes are listed in MARPOL Annex I - Appendix I, and NLS cargoes carried in bulk are listed in Chapter 19 of the IBC Code. 2.2 The Basic Chemistry of Bulk Liquid Chemical Cargoes It is not the aim of this book to qualify the ship’s officer as a chemical engineer, however in the application of theory, it is important to grasp the fundamental chemistry behind the products and the manufacturing processes. This section provides some basic chemistry descriptions and forms a foundation for the next section and following Chapters. 2.2.1 Organic Chemical Characteristics Hydrocarbons, which are compounds of carbon and hydrogen, are among the most important organic compounds. The hydrogen atoms are attached to the carbon backbone in varying numbers. The simplest example of a hydrocarbon is methane, which is naturally occurring and sometimes referred to as swamp or marsh gas. Methane will be referred to by its molecular formula CH4. This means that each carbon atom has 4 atoms of hydrogen. Ethene (ethylene), whose molecular formula is C2H4, is commercially produced from the cracking of fractions obtained from the distillation of natural gas and oil. Its formula indicates that it has 2 atoms of carbon and 4 atoms of hydrogen. It is important to understand the importance of the physical properties of methane, ethene 9 Chemical Cargoes and the Basic Chemistry and a third hydrocarbon, known as ethyne (acetylene) C2H2. Many chemical compounds, and particularly hydrocarbons, can exist in different geometric configurations. Some compounds can have the same molecular formula but be linked together in different ways. A structural formula allows the arrangements of atoms to be shown in a way that a chemical formula cannot. This is important because the structure of the molecule depicts how strong the links are that bind the compound together. The stronger the links, the more stable is the compound. An important concept to grasp, before continuing to look at molecular structure, is the ‘valence’. This is also known as the valency or valency number, which is a measure of the number of chemical bonds (arms) formed by atoms of the element. A simple method is to imagine the carbon atom as an object with 4 ‘arms’, which would make the valency number ‘4’. Carbon atom C Figure 2.1 – Carbon atom with 4 arms CH4 methane CH HH H Figure 2.2 – Carbon atom with each arm holding a hydrogen atom C2H4 ethene CCH HH H Figure 2.3 – Two carbon atoms holding each other in addition to hydrogen atoms At all times, each of the arms should be holding on to something, by preference it will hold onto the arm of another atom that is different to itself. However, when there is no alternative, it will hold onto another like itself. Being bonded to another carbon atom will always make a structure like the one in Figure 2.3 less stable. So the CH4 structure in Figure 2.2 is very stable and will stay that way in most pressure and temperature conditions. Most ‘Stable’ Methane CH4 Ethene C2H4(ethylene) Ethyne C2H2(acetylene) Least ‘Stable’ Figure 2.4 – Structural formula 13 Chemical Cargoes and the Basic Chemistry Ethylene VCMPVC pipes, plates, synthetic leather Gasoline, Jet Fuel / Kerosene, Diesel, Fuel Oil, Base Oil, Asphalt Naphtha VAM P-Xylene Toluene Benzene Butadiene Propylene AN SM EG Phenol IPA Poly- epoxide Acrylates Polystyrene products andthermos lining Fabric film Sports shoesand equipment Fabric, fibre board, auto parts Coatings, nylon Paint, ink, nitrocellulose Paints, adhesives, plastic moulding Glues, resins and paint Synthetic fleece, clothes, toys Home electrical Tyres PTAPolyester Solvent, paint, coatings Food containers, electricalcasing Auto parts, helmets, suitcase mouldings Epoxy, nylon SM Phenol LNG Methane NGL LPG Crude Oil Figure 2.6 – The end products of petrochemical manufacturing Chapter 2 Regulations, Codes and Industry Guidelines MARPOL Annex I MARPOL Annex II IBC Code IGC Code 17 3 The Regulations 3.1 The International Maritime Organization Formally established in 1948 by an international conference meeting in Geneva, the IMO Convention entered into force in 1958. With its headquarters on the south bank of the River Thames in London, the IMO is a specialized agency of the United Nations and promotes safe, secure, environmentally sound, efficient and sustainable shipping through the cooperation of Member States. The universal and uniform implementation of IMO instruments achieves the highest practicable standards of maritime safety and security, efficiency of navigation and prevention and control of pollution from ships. Member States implement the IMO Regulations by adoption into their own national laws and use their Port State Control to ensure that ships calling at their ports are compliant with the international regulations. Some Member States are land-locked and do not have a coastline, however they have a significant role in maritime affairs, either through management, finance or crewing. Not all countries are members of the IMO and not all Members are signatory to all Conventions. For whatever reason, international trade without compliance with the IMO Conventions would be virtually impossible. 3.1.1 The Structure of the IMO To properly understand the Conventions and the international regulations, it is important to have an overview of the Committee and Sub-Committee structure of the IMO. yyThe General Assembly Consisting of all Member States, the Assembly is the governing body of the IMO. Meeting every two years, the Assembly approves the work programme and controls the financial affairs. The Assembly elects the Members of the Council. yyThe Council Made up of the elected Members, the Council is in effect the Executive level of the IMO organisation and supervises the work programme as set out by the Assembly. Meeting once per year, the Council assess the work programme and budget requirements, preparing the estimates and recommendations for submission to the Assembly. yyThe Maritime Safety Committee (MSC) All Member States are represented on the MSC and “consider any matter within the scope of the Organization concerned with aids to navigation, construction and equipment of vessels, manning from a safety standpoint, rules for the prevention of collisions, handling of dangerous cargoes, maritime safety procedures and requirements, hydrographic information, log-books and navigational records, marine casualty investigations, salvage and rescue and any other matters directly affecting maritime safety”. yyMarine Environment Protection Committee (MEPC) Similar to MSC, all Member States are represented on the MEPC which is responsible for considering any matter related to prevention and control of pollution from ships. MEPC works closely with MSC ensuring harmony between the SOLAS and MARPOL Conventions and the application of the regulations governing design, construction and operations. 29 4 Chemical Cargo Hazards In order to align the chemical regulations and standards of different countries, the United Nations adopted the Globally Harmonized System (GHS) of the Classification and Labelling of Chemicals which is periodically updated. It provides guidelines on safe production, transportation, handling, use and disposal of hazardous materials. All countries are expected to adopt the guidelines of the GHS into their own chemical management systems, making the international transportation of hazardous chemicals, easier and safer for all those exposed to chemical hazards. The GHS is not a global law or regulation and therefore no country is obligated to adopt all or even any part of the GHS. The implementation of the GHS in the European Union (EU) in 2008 makes the EU a front-runner in its uptake. The Occupational Health and Safety Administration (OSHA) is part of the United States Department of Labour which ensures that businesses provide a safe workplace that is free from recognized hazards, promoting health and safety in the workplace, and bringing about a reduction in the occurrence of on the job injuries, illnesses, and fatalities. OSHA adopted the GHS on 26 March 2012 that brought about a revision of the Hazard Communication Standard (HCS) to align with the GHS and called HazCom 2012. 4.1 Safety Data Sheets Safety Data Sheets (SDS), Material Safety Data Sheets (MSDS), and Product Safety Data Sheets (PSDS) are issued in different formats by the manufacturers to provide specific safety information to all users and service providers involved in the handling, storage and transportation of the products. In the revision of the Hazard Communication Standard (HCS) in 2012, the letter ‘M’ was dropped out from MSDS in the GHS, calling it Safety Data Sheet (SDS) and giving it a structured format of 16 mandatory sections. Sections 1 through 8 contain general information about the chemical, identification, hazards, composition, safe handling practices, and emergency control measures (e.g., fire-fighting). This information should be helpful to those that need to get the information quickly. Sections 9 through 11 and 16 contain other technical and scientific information, such as physical and chemical properties, stability and reactivity information, toxicological information, exposure control information, and other information including the date of preparation or last revision. The SDS should also state that no applicable information was found when the preparer does not find relevant information for any required element. Sections 12 through 15 provide ecological, disposal, transportation and regulatory information of the product. It is important that the SDS is unique and specific to the product; this is particularly relevant for organic chemicals which can differ widely in their physical properties from one geographical area to another. Whilst not the manufacturer, SDS are often transposed and re-issued by the shipper who is responsible for providing the information to the ship. Very often the complete SDS will not be available with the voyage orders; however, the ship should receive all relevant information for cargo planning. The SDS should be on board the ship prior to loading the cargo. The sections of the SDS are designed to provide sufficient information for the custodian to handle the product in a safe manner and respond accordingly to any response situation. The information required by GHS under each section of the SDS are listed in the table below. 30 Chemical Tanker Operations for the STCW Advanced Training Course Safety Data Sheet 1.Product Identification a) Product name b) Other means of identification, e.g., synonyms c) Recommended use of the chemical and restrictions on use Supplier’s details (including name, address, phone number etc.) d) Emergency phone number. 2.Hazard(s) identification a) GHS classification of the substance/mixture and any national or regional information b) GHS label elements, including precautionary statements. (Hazard symbols may be provided as a graphical reproduction of the symbols in the black and white or the name of the symbol e.g. “flame”, “skull and crossbones”) c) Other hazards which do not result in the classification (e.g. “dust explosion hazard”) or are not covered by the GHS. 3.Composition/Information on Ingredients Substance a) Chemical identity b) Common name, synonyms, etc. c) CAS number and other unique identifiers d) Impurities and stabilizing additives which are themselves classified and which contribute to the classification of a substance. Mixture The chemical identity and concentration or concentration ranges of all ingredients which are hazardous within the meaning of the GHS and are present above their cut-off levels. Note: The exact concentration percentage of each ingredient must be specified with the following exceptions where concentration ranges may be used instead: yy When a trade secret claim is made through a statement that the specific chemical identity and/or exact percentage (concentration) of composition has been withheld as a trade secret, or yyWhen there is batch-to-batch variation, or yyWhen the SDS is used for a group of substantially similar mixtures. 4.First aid measures a) Description of necessary measures, subdivided according to the different routes of exposure, i.e. inhalation, skin and eye contact and ingestion b) Most important symptoms/effects, acute and delayed c) Indication of immediate medical attention and special treatment needed, if necessary. 5.Firefighting measures a) Suitable (and unsuitable) extinguishing media b) Specific hazards arising from the chemical (e.g. nature of any hazardous combustion products) c) Special protective equipment and precautions for fire-fighters. 6.Accidental release measures a) Personal precautions, protective equipment and emergency procedures b) Environmental precautions c) Methods and materials for containment and cleaning up. 7.Handling and storage a) Precautions for safe handling b) Conditions for safe storage, including any incompatibilities. 8.Exposure controls/personal protection a) Control parameters e.g. occupational exposure limit values or biological limit values b) Appropriate engineering controls c) Individual protection measures, such as personal protective equipment. 9.Physical and chemical properties a) Appearance (physical state, colour etc.) b) Odour c) Odour threshold d) pH e) Melting point/freezing point f) Initial boiling point and boiling range 32 Chemical Tanker Operations for the STCW Advanced Training Course This book will continuously reference the SDS and following chapters will expand on the information contained in the document. After discharge and tank cleaning, a copy of the SDS should be retained with the voyage papers, however extreme caution should be exercised in using the same document again. 4.1.1 Hazard Warning Symbols Though usually associated with packaged goods, hazard warning symbols are used on board chemical tankers to warn personnel of dangerous areas and hazardous contents. The modern system of hazard warning pictographs adopts the Globally Harmonised System (GHS) of a diamond shape with white background, black symbols and a red border. Flame over circle Oxidisers Acute Toxicity (severe)CorrosivesGases Under Pressure Irritant Dermal Sensitiser Acute Toxicity (harmful) Narcotic Effects Respiratory Tract Irritation Environmental ToxicityCarcinogen Respiratory Sensitiser Reproductive Toxicity Target Organ Toxicity Mutagenicity Aspiration Toxicity Flammables Self-Reactives Pyrophorics Self-Heating Emits Flammable Gas Organic Peroxides Explosives Self-Reactives Organic Peroxides FlameExploding bomb Skull and crossbonesCorrosionGas cylinder Health hazardEnvironmentExclamation mark Figure 4.1 – The GHS hazard warning pictographs 4.2 Fire and Explosion The basic difference between a fire and an explosion is the rate of reaction. A fire reaction can continue over a long period, but an explosion is a reaction of short duration. Fire During combustion, the rate of energy release is in balance with the dissipation of this energy. This means that, over time, a limiting rate of reaction is reached. This can be observed in Figure 4.2 with the combustion line levelling off. Time Explosion Combustion Rate of Reaction Figure 4.2 – Rate of reaction over time Explosion During an explosion, the products of combustion remain in the reaction zone, meaning that the temperature and pressure continue to rise. The rate of reaction increases exponentially until all the reactants are consumed. 4.2.1 Requirements for a Fire or Explosion Before a fire or explosion can take place, the three elements that must be present, commonly known as the ‘fire triangle’ are: yyA flammable material capable of supporting combustion (fuel) yya source of ignition with sufficient energy to initiate combustion (heat) yyan adequate supply of oxygen, usually air (oxidiser). Fire Triangle FuelOxygen Heat Figure 4.3 – The fire triangle